EP0390912A1 - Faserförmige aktivkohlen - Google Patents

Faserförmige aktivkohlen

Info

Publication number
EP0390912A1
EP0390912A1 EP89911998A EP89911998A EP0390912A1 EP 0390912 A1 EP0390912 A1 EP 0390912A1 EP 89911998 A EP89911998 A EP 89911998A EP 89911998 A EP89911998 A EP 89911998A EP 0390912 A1 EP0390912 A1 EP 0390912A1
Authority
EP
European Patent Office
Prior art keywords
carbon
acid
boron
phosphorus
containing compound
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP89911998A
Other languages
English (en)
French (fr)
Inventor
John Michael Devereux De La Pena
Richard Adrian Roberts
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
WOODVILLE POLYMER ENGINEERING Ltd
Original Assignee
WOODVILLE POLYMER ENGINEERING Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by WOODVILLE POLYMER ENGINEERING Ltd filed Critical WOODVILLE POLYMER ENGINEERING Ltd
Publication of EP0390912A1 publication Critical patent/EP0390912A1/de
Withdrawn legal-status Critical Current

Links

Classifications

    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F11/00—Chemical after-treatment of artificial filaments or the like during manufacture
    • D01F11/10—Chemical after-treatment of artificial filaments or the like during manufacture of carbon
    • D01F11/12—Chemical after-treatment of artificial filaments or the like during manufacture of carbon with inorganic substances ; Intercalation
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F11/00—Chemical after-treatment of artificial filaments or the like during manufacture
    • D01F11/10—Chemical after-treatment of artificial filaments or the like during manufacture of carbon
    • D01F11/12—Chemical after-treatment of artificial filaments or the like during manufacture of carbon with inorganic substances ; Intercalation
    • D01F11/124—Boron, borides, boron nitrides
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
    • D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
    • D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
    • D01F9/14—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
    • D01F9/16—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from products of vegetable origin or derivatives thereof, e.g. from cellulose acetate

Definitions

  • the invention relates to the manufacture of fibrous or film-type activated carbons which can be used as supports for catalysts or for the adsorption of
  • Processes for producing fibrous or film-type activated carbons have been known for some years. Such processes chiefly comprise carbonising fibrous organic starting materials by heating in an inert atmosphere to drive off volatile matter and then 'activating' the material to form the desired porous active surface in the carbonised fibrous material (char) by further heating to a temperature higher than the carbonising
  • G3 Patent No. 1455531 An improved activated carbon fibre material having high adsorbancy and superior physical strength is also disclosed in G3 Patent No. 1455531 in which during manufacture a cellulose fibre is impregnated with a phosphorus compound prior to carbonisation. More recently, in GE-A-2164327, a process has been described for making an activated carbon fibrous material having a substantial percentage of mesopores in which pre- treatment comprises impregnation with one or more compounds of boron and at least one alkali metal.
  • At least one boron-containing compound and at least one phosphorus-containing compound are preferably at least one boron-containing compound and at least one phosphorus-containing compound.
  • the boron- containing compound may be an acid or a salt.
  • phospnorus containing compounds are acids such as phosphoric acid, metaphosphoric acid, pyrophosphoric acid, phosphorus acid, phosphonic acid, phosphonous acid, phosphinic acid and phosphinous acid, or their salts, or phosphonium salts, phosphines and phosphine oxides.
  • the impregnation preparation may contain a mixture of several of the aforementioned boron
  • the boron and phosphorus compounds which form the impregnating preparation may be impregnated onto or into the carbon by contacting the carbon with the impregnating preparation when the preparation is dissolved in a solvent and then drying the carbon leaving the boron and phosphorus compounds incorporated therein or as an external coating on the surface .
  • the impregnation preparation should preferably be acidic in solution.
  • acids of boron and phosphorus preferred solvents are water, ethanol, methanol, propanol, glycerol, acetate, isoamyl alcohol, ethylene giycol, and diethylether.
  • phosphorus or boron preferred solvents are mineral acids or formic acid.
  • the drying step may be effected at room temperature or more preferably the impregnated material is placed in a drying oven between the temperatures of 40°C and 200°C in either air or vacuum or an inert gas.
  • the total concentration of boron compounds dissolved or suspended in the solvent is preferably from 0.1% to 4.5% w/v (weight/volume) and particularly from 1 to 4%, while the total concentration of dissolved or suspended phosphorus compounds is preferably from 0.1% to
  • the impregnation of the carbon takes place prior to carbonisation although this is not essential.
  • the amount of boron and phosphorus impregnated onto or into the carbon may be from 0.01 to 20% and preferably from 0.1 to 10% by weight of carbon.
  • the carbon can be carbonised and activated using well-known methods.
  • the carbon is first heated to temperatures between 200oC and 850°C to effect carbonisation and drive off
  • Both the carbonisation and activation takes place in an inert atmosphere which will usually contain one of the following, for example, nitrogen, noble gas, argon, helium, hydrogen, carbon monoxide, carbon dioxide, combustion gas from hydrocarbon fuels, steam, and hydrogen or any mixture thereof. These gases are particularly favoured because they suppress oxidation and combustion of the activated fibrous carbon.
  • the inert atmosphere is usually carbon dioxide, steam, hydrogen or a mixture thereof.
  • Carbons receiving the impregnation treatment of the invention may equally well undergo carbonisation and activation in a batch furnace such as that described for example in GB Patent No. 1570677 or in a furnace adapted for continuous feed such as that described in GB Patent No. 1310011.
  • the fibrous or film-type carbon product may be in the form of filament, yarn, thread or tow, or knitted or woven or non-woven cloth, film, felt or sheets.
  • Suitable starting materials for the process of the invention include cellulosic material such as rayon, wool, lignin, viscose, wood pulp, cotton, paper, or coal base, nut shell or nut kernel, or seed pips and also man-made organic polymers or any composite of any of the above. Some of these fibrous materials may be rendered stiff and inflexible by the impregnation treatment and a softening step will be required.
  • Impregnation of the carbon starting materials with compounds of phosphorus and boron in accordance with the invention produce carbonisation yields between 20% and 40% when the impregnation solution is acid.
  • Activation times are generally between 1 and 240 minutes but activation is preferably continued until the carbon has an apparent surface area in excess of 700m 2 g -1 .
  • the activation yield is preferably between 25% and 95% with the percentage 'burn-off' during activation being between 5% and 75%.
  • the process of the invention produces a product which is highly microporous and as the percentage burn-off increases so an increase in micropore size distribution is achieved.
  • the process of the invention being capable of producing an activated carbon having a hon-microporous area between 20-70 m 2 g -1 .
  • mesoporous material is particularly useful as a
  • catalyst support On the other hand highly microporous material is preferred for adsorption and filtration applications.
  • adsorption/desorption hysteresis isotherms for similar samples of activated carbon cloth according to the invention but manufactured with different percentage burn-offs.
  • Each sample was immersed in the impregnation solution for 30 seconds, dried on blotting paper to remove excess solut and then dried in an oven at 55°C.
  • the dried sample was suspended in a vertical tube furnace and pyrolysed in a stream of inert gas.
  • the weight loss of the sample during pyrolysis can be continuously measured by a calibrated electronic balance mounted on a frame above the furnace.
  • Pyrolysis involved a carbonisation stage during which the sample was heated from ambient temperature at a rate of 10°C per minute to 850°C in a flow of nitrogen gas. This was followed by an activation stage during which the inert gas was changed to carbon dioxide and the furnace temperature maintained at 850°C for a sufficient length of time to achieve a desired
  • the impregnation solution used in each example was an aqueous solution of phosphoric acid and boric acid in the particular amounts quoted by percentage weight per volume (w/v) in the Table below.
  • the characteristics of the pore structure of the final samples of activated carbon cloth are determined from adsorption/desorption hysteresis isotherms at 77°K obtained by subjecting the cloth to an increasing pressure of nitrogen gas so as to cause increasing amounts of nitrogen to adsorb onto the carbon, and then decreasing the pressure of nitrogen to cause the nitrogen to desorb from the carbon.
  • the nitrogen pressure p is measured as a fraction (p/p o ) of the saturated vapour pressure p° of nitrogen at the
  • BET area Brunnauer, Emmett and Teller
  • V ⁇ V 0.95 0.00156 cm 3 /gram.
  • V 0.95 is the value of the nitrogen amount read off the isotherm at the nitrogen pressure p/p o of 0.95.
  • the carbonisation percentage yield was also measured based on the weight of the sample before and after carbonisation, and the result for each
  • activated carbon cloth were also measured in terms of tensile strength in Newtons/2.5cm, and percentage

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Carbon And Carbon Compounds (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Inorganic Fibers (AREA)
  • Chemical Treatment Of Fibers During Manufacturing Processes (AREA)
  • Catalysts (AREA)
EP89911998A 1988-09-26 1989-09-26 Faserförmige aktivkohlen Withdrawn EP0390912A1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB8822518 1988-09-26
GB888822518A GB8822518D0 (en) 1988-09-26 1988-09-26 Improvements in & relating to fibrous activated carbons

Publications (1)

Publication Number Publication Date
EP0390912A1 true EP0390912A1 (de) 1990-10-10

Family

ID=10644216

Family Applications (1)

Application Number Title Priority Date Filing Date
EP89911998A Withdrawn EP0390912A1 (de) 1988-09-26 1989-09-26 Faserförmige aktivkohlen

Country Status (5)

Country Link
US (1) US5202302A (de)
EP (1) EP0390912A1 (de)
JP (1) JPH03501509A (de)
GB (2) GB8822518D0 (de)
WO (1) WO1990003458A1 (de)

Families Citing this family (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5346389A (en) * 1989-02-24 1994-09-13 W. R. Grace & Co.-Conn. Combustion apparatus for high-temperature environment
FI85133C (fi) * 1990-06-27 1992-03-10 Kemira Oy Saeteri Foerfarande foer framstaellning av aktivkol fraon cellulosahaltigt material.
FI86403C (fi) * 1990-10-23 1992-08-25 Kemira Oy Saeteri Foerfarande foer framstaellning av aktivkol fraon cellulosahaltigt material.
US6277780B1 (en) * 1994-08-09 2001-08-21 Westvaco Corporation Preparation of phosphorus-treated activated carbon composition
US6057262A (en) * 1995-05-19 2000-05-02 University Of Kentucky Research Foundation Activated carbon and process for making same
US5926361A (en) * 1995-09-28 1999-07-20 Westvaco Corporation High power density double layer energy storage devices
US6043183A (en) * 1995-09-28 2000-03-28 Westvaco Corporation High power density carbons for use in double layer energy storage devices
US5905629A (en) * 1995-09-28 1999-05-18 Westvaco Corporation High energy density double layer energy storage devices
US6060424A (en) * 1995-09-28 2000-05-09 Westvaco Corporation High energy density carbons for use in double layer energy storage devices
CN1077926C (zh) * 1999-06-11 2002-01-16 中山大学 硼酸活化法制备活性碳纤维的工艺
US6599856B1 (en) * 1999-10-21 2003-07-29 Tennex Corporation Formed activated carbon and process for producing the same
EP1622830A2 (de) * 2003-05-09 2006-02-08 McGill University Verfahren zur herstellung von aktivkohle
US8313723B2 (en) * 2005-08-25 2012-11-20 Nanocarbons Llc Activated carbon fibers, methods of their preparation, and devices comprising activated carbon fibers
US20070178310A1 (en) 2006-01-31 2007-08-02 Rudyard Istvan Non-woven fibrous materials and electrodes therefrom
WO2007120386A2 (en) * 2006-02-15 2007-10-25 Rudyard Lyle Istvan Mesoporous activated carbons
RU2472702C2 (ru) * 2007-02-14 2013-01-20 Университи оф Кентукки Ресеарч Фоундатион Инк. Способы формирования активированного углерода
WO2008112306A1 (en) * 2007-03-14 2008-09-18 Tucker Richard D Pyrolysis systems, methods, and resultants derived therefrom
US9604192B2 (en) 2007-03-14 2017-03-28 Richard D. TUCKER Pyrolysis and gasification systems, methods, and resultants derived therefrom
CN102817112B (zh) * 2012-09-11 2014-10-15 长春高琦聚酰亚胺材料有限公司 一种纤维活性炭的制备方法
CN103551115A (zh) * 2013-09-25 2014-02-05 蚌埠德美过滤技术有限公司 一种硼酸改性活性炭及其制备方法
JP6769964B2 (ja) * 2014-12-11 2020-10-14 ストラ エンソ オーワイジェイ 粉末としてリグノセルロース系材料を炭化する新規方法
CN116553543A (zh) * 2023-05-18 2023-08-08 福建省鑫森炭业股份有限公司 一种低温预处理磷酸法制备活性炭的方法
CN117418334B (zh) * 2023-11-02 2026-01-20 中国人民解放军军事科学院防化研究院 一种硼掺杂的聚丙烯腈基活性碳纤维及其制备方法

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1267201A (de) * 1968-10-03 1972-03-15
US3969268A (en) * 1974-12-31 1976-07-13 Toyobo Co., Ltd. Process for preparing active carbon fibers
GB1455531A (en) * 1975-01-02 1976-11-10 Toyo Boseki Process for preparing active carbon fibres machine for attaching components to a printed circuit board
JPS602408B2 (ja) * 1977-08-17 1985-01-21 東邦ベスロン株式会社 耐熱酸化性の優れた炭素繊維
DE3214948A1 (de) * 1981-04-23 1982-11-25 Toho Beslon Co., Ltd., Tokyo Verfahren zur herstellung von aktivierten kohlenstoffasern
GB8422875D0 (en) * 1984-09-11 1984-10-17 Secr Defence Fibrous activated carbon
JPS6215645A (ja) * 1985-07-15 1987-01-24 Toshiba Corp 中央処理装置

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9003458A1 *

Also Published As

Publication number Publication date
US5202302A (en) 1993-04-13
GB8822518D0 (en) 1988-11-02
JPH03501509A (ja) 1991-04-04
WO1990003458A1 (en) 1990-04-05
GB2225003B (en) 1992-07-08
GB8921715D0 (en) 1989-11-08
GB2225003A (en) 1990-05-23

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